EP1950244B1 - Light-scattering compositions - Google Patents

Light-scattering compositions Download PDF

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Publication number
EP1950244B1
EP1950244B1 EP08250237A EP08250237A EP1950244B1 EP 1950244 B1 EP1950244 B1 EP 1950244B1 EP 08250237 A EP08250237 A EP 08250237A EP 08250237 A EP08250237 A EP 08250237A EP 1950244 B1 EP1950244 B1 EP 1950244B1
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Prior art keywords
light
diffuser
polymer particles
scattering composition
particle size
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German (de)
English (en)
French (fr)
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EP1950244A1 (en
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Edward E. Lafleur
Jiun-Chen Wu
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Rohm and Haas Co
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Rohm and Haas Co
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/22Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08Homopolymers or copolymers of acrylic acid esters
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to light-scattering compositions and methods of making and using the same.
  • the present invention relates to light-scattering compositions comprising diffuser polymer particles.
  • Light-diffusing polymers are often "semi-transparent" or translucent to visible light, that is, they scatter transmitted light, preferably without significantly reducing its intensity. They may be clear or colored, and may be incorporated into clear or colored thermoplastic or thermoset polymer matrices to form light-scattering thermoplastic or thermoset polymer compositions which may be formed into sheets or films of various thicknesses, or into more complex shapes.
  • compositions find use as light diffusers in, for example, luminaires, rear projection screens for television or film viewing, decoration, illuminated signs (especially back-lit translucent signs), skylight, lighting fixtures (especially for fluorescent or incandescent lighting), greenhouse glazing, light boxes, drafting tables, automotive sunroofs, artistic applications (e.g., as visual display-case components), antiglow screens for CRT units, twin-wall glazing and covers for automotive lights.
  • Japanese Patent Publication No. 64-10515 discloses a method for producing a translucent resin comprising mixing fine particles of a bridging polymer in a transparent resin of a base material, said bridging polymer particles having an average diameter of 0.5 to 5 m and differing in refractive index from the matrix by 0.05 to 0.3 units.
  • the reference requires a bridging monomer which is a crosslinking monomer.
  • thermoplastic composition having modified optical properties discloses a thermoplastic composition having modified optical properties.
  • Wu et al. disclose a thermoplastic composition having modified optical properties which comprises a thermoplastic matrix polymer and, distributed throughout the matrix polymer, from about 0.1 % to about 40 % of the total composition weight of spherical polymer particles of core/shell having an average diameter of from about 2 to about 15 m and a size distribution such that at least 90% by weight of the polymer particles fall within 20% of the average particle diameter, a core of rubbery alkyl acrylate polymer and one or more shells, the outer shell of which is compatible with the matrix polymer.
  • JP-A-2006/084927 discloses a light diffusing agent and a manufacturing method.
  • the light diffusing agent comprises spherical organic polymer fine particles having a smaller average particle size and a different refractive index dispersed in an island structure.
  • JP-A-2006/023350 discloses an antireflection film polarising a plate and image display device.
  • the antireflection film is made by applying at least one diffusion layer and antistatic layer and a lower refractive index layer having a refractive index lower than that of a transparent substrate.
  • a light-scattering composition comprising diffuser polymer particles; wherein the diffuser polymer particles have an average particle size of 0.3 to 1.9 ⁇ m; wherein the diffuser polymer particles comprise C 2 to C 8 alkyl acrylate monomers copolymerised with > 4wt% to 99wt% crosslinking monomers; wherein the diffuser polymer particles exhibit a different refractive index at a center thereof (RIcenter) than at a surface thereof (RIsurface); wherein RIcenter ⁇ RIsurface; and, wherein the diffuser pdymer particles are single phase particles, that is particles having a gradual increase in refractive index from the centre to the surface.
  • a light-scattering composition comprising a matrix polymer and diffuser polymer particles; wherein the diffuser polymer particles have an average particle size of 0.3 to 1.9 ⁇ m; wherein the diffuser polymer particles are distributed throughout the matrix polymer and wherein the diffuser polymer particles comprise 0.1 to 10 wt% of the light-scattering composition.
  • a flat panel display having a diffusion layer comprising a light-scattering composition of the present invention, wherein the diffusion layer is 0.45 mm to 4 mm thick.
  • a lighting diffuser comprising a light-scattering composition of the present invention.
  • copolymer refers to polymers polymerized from at least two different monomers.
  • average particle size is the d 50 value measured on a Malvern Instruments particle size analyzer Mastersizer 2000.
  • RI center refers to the refractive index measured at the center of the diffuser polymer particles in glycerol using a Zeiss Jenaval Interphako Interference Microscope.
  • RI surface refers to the refractive index measured at the surface of the diffuser polymer particles in glycerol using a Zeiss Jenaval Interphako Interference Microscope.
  • single phase as used herein and in the appended claims in reference to the diffuser polymer particles means that the subject particles exhibit a gradual increase in RI from the center to the surface.
  • single phase refers to the "as made" diffuser polymer particles.
  • the diffuser polymer particles can in certain situations be modified upon combination with the matrix polymer.
  • the diffuser polymer particles and the matrix polymer can in certain situations interact to form a shell like structure at the interface between the diffuser polymer particles and the matrix polymer.
  • monovinyl arenes used herein and in the appended claims encompasses monoethylenically unsaturated aromatic monomers including styrene, alkylstyrenes (e.g., methylstyrene and ethylstyrene), other substituted vinylbenzenes wherein the substitutents do not interfere with polymerization, and vinyl polycyclic aromatic monomers.
  • the matrix polymer is selected from thermoplastic polymers, thermoset polymers and combinations thereof. In some aspects of these embodiments, the matrix polymer is selected from translucent polymers and transparent polymers. In some aspects of these embodiments, the matrix polymer is selected from transparent polymers that have a glass-transition temperature ⁇ 50 °C. In some aspects of these embodiments, the matrix polymer is selected from polymers that are amorphous following incorporation of the diffuser polymer particles of the present invention, and that remain amorphous following processing to form a light-scattering composition of the present invention.
  • the matrix polymer exhibits an elastic modulus of 1,400 to 3,500 MegaPascals (MPa).
  • the matrix polymer is capable of being formed into shaped articles by molding, casting, extrusion or other processes apparent to one of ordinary skill in the art.
  • the light scattering composition is formed into a film or sheet.
  • the film has an average thickness of 21 to 250 ⁇ m. In some aspects of these embodiments, the film has an average thickness of 70 to 125 ⁇ m. In some aspects of these embodiments, the sheet has a thickness of 0.45 to 4 mm. In some aspects of these embodiments, the sheet has a thickness of 0.5 to 3 mm.
  • the matrix polymer is prepared from chain growth polymerization or step growth polymerization.
  • the matrix polymer is produced using or comprises materials selected from acrylonitrile-butadiene-styrene (ABS), polyolefins, polycarbonates, polycarbonate-polyester blends, polyamides, poly(alkylene terephthalates), polystyrene, cyclo-olefins, polystyrene/methacrylate blends, and combinations thereof.
  • ABS acrylonitrile-butadiene-styrene
  • polyolefins polycarbonates
  • polycarbonate-polyester blends polyamides
  • poly(alkylene terephthalates) polystyrene
  • cyclo-olefins polystyrene/methacrylate blends
  • the matrix polymer is produced using or comprises materials selected from acrylonitrile-butadiene-styrene (ABS), polyolefins, polycarbonates, polycarbonate-polyester blends, polyamides, poly(alkylene terephthalates), polystyrene, cyclo-olefins and polystyrene/methacrylate blends.
  • ABS acrylonitrile-butadiene-styrene
  • polyolefins polycarbonates
  • polycarbonate-polyester blends polyamides
  • poly(alkylene terephthalates) polystyrene
  • cyclo-olefins polystyrene/methacrylate blends.
  • the matrix polymer is selected from polymethyl methacrylate, polystyrene, styrene-acrylonitrile compolymers, polystyrene methacrylate copolymers, styrene-methyl methacrylate copolymers, olefin-vinyl acetate copolymers, polymethylpentene, polyethylene, polypropylene, copolymers of polyethylene and polypropylene, polyglutarimide, styrene-maleic anhydride copolymers, cyclic olefin copolymers and combinations thereof.
  • the matrix polymer is produced using materials selected from alkyl (alkyl)acrylate, vinyl aromatics, vinyl chloride, cellulose acetate butyrate, poly(ethylene terepthalate), poly(cyclohexanedimethanol terephthalate), derivatives thereof, copolymers thereof and refractive index matched blends thereof.
  • the matrix polymer is produced using materials selected from copolymers of methyl methacrylate with alkyl acrylates, styrene with up to 40wt% acrylonitrile, styrene with methyl methacrylate, alpha-methylstyrene with methyl methacrylate and alkyl acrylates, vinyl chloride and vinyl acetate, vinyl chloride and propylene.
  • the alkyl acrylates are selected from C 1-8 alkyl acrylates and derivatives thereof.
  • the matrix polymer is produced using materials selected from a copolymer of methyl methacrylate with 1 to 15wt% C 1-8 alkyl acrylate.
  • the matrix polymer is produced using materials selected from poly(vinyl acetate), plasticized vinyl chloride homopolymers, plasticized vinyl chloride copolymers and plasticized cellulosic esters.
  • the matrix polymer is produced using materials selected from thermoset polymers.
  • the matrix polymer is thermoset as prepared (e.g., such as in casting of a sheet of poly(methyl methacrylate) containing sufficient polyfunctional monomer to immobilize and insolubilize the resulting sheet).
  • the matrix polymer is rendered thermoset during subsequent processing (e.g., after initial polymerization is completed such as by activating a cure reaction by heating of the initially polymerized sheet).
  • the matrix polymer is produced using materials selected from methyl methacrylate, styrene, vinyl chloride, imidized polymers of methyl methacrylate (known as polyglutarimides), copolymers of methyl methacrylate with alkyl acrylates, copolymers of styrene with up to 40% acrylonitrile, copolymers of styrene with methyl methacrylate, copoymers of alpha-methylstyrene with methyl methacrylate and alkyl acrylates; copolymers of vinyl chloride with vinyl acetate and coplymers of vinyl chloride with propylene.
  • the matrix polymer is produced using compatible or refractive-index matched polymer blends. In some aspects of these embodiments, the matrix polymer is produced using materials selected from copolymers of methyl methacrylate with 1 to 15wt% alkyl acrylates. In some aspects of these embodiments the alkyl acrylates are selected from C 1-8 alkyl acrylates. In some aspects of these embodiments, the matrix polymer is further derived or produced using a polyfunctional dimethacrylate. In some aspects of these embodiments, the matrix polymer is further derived or produced using 0.05 to 2 wt% polyfunctional dimethacrylate.
  • the matrix polymer is further derived or produced using acrylamide and N-methylolacrylamide. In some aspects of these embodiments, the matrix polymer is further derived or produced using 0.05 to 5 wt% acrylamide and N-methylolacrylamide.
  • the matrix polymer is selected from polymers formed through condensation reactions and/or ring-opening reactions. In some aspects of these embodiments, the matrix polymer is produced through polyesterification in the presence of multifunction glycols or by epoxide polymerization in the presence of trifunctional epoxides.
  • the matrix polymer is an optical grade material.
  • the matrix polymer has a refractive index of from 1.49 to 1.59.
  • the matrix polymer has a yellowness index of ⁇ 1.
  • the matrix polymer has a haze of ⁇ 1 %.
  • the matrix polymer has a yellowness index of ⁇ 1 and a haze of ⁇ 1 %.
  • the diffuser polymer particles are produced using step reaction or chain growth polymerization. In some aspects of these embodiments, the diffuser polymer particles are produced using one or more vinyl monomers. In some aspects of these embodiments, the diffuser polymer particles comprise rubbery polymers. In some aspects of these embodiments, the diffuser polymer particles comprise glassy polymers. In some aspects of these embodiments, the diffuser polymer particles are produced through free-radical initiated polymerization.
  • the diffuser polymer particles are prepared through polymerization or copolymerization of monomers selected from diolefins (e.g., butadiene, isoprene); vinyl aromatic monomers (e.g., styrene, chlorostyrene); vinyl esters (e.g., vinyl acetate, vinyl benzoate); acrylonitrile; methylacrylonitrile; (meth)acrylate esters (e.g., methyl methacrylate, butyl methacrylate, phenyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate); and vinyl chloride.
  • the alkyl acrylate derivatives include halogenated species for example chlorinated species and fluorinated species.
  • the diffuser polymer particles are selected from rubbery alkyl acrylate polymers. These diffuser polymer particles are produced using C 2-8 alkyl acrylate monomers copolymerized with > 4 wt% to 99 wt% crosslinking monomer(s). In some aspects of these embodiments, the diffuser polymer particles are produced using C 2-8 alkyl acrylate monomers copolymerized with > 4 wt% to 50 wt% crosslinking monomer(s). In some aspects of these embodiments, the diffuser polymer particles are produced using C 2-8 alkyl acrylate monomers copolymerized with 5 wt% to 10 wt% crosslinking monomer(s).
  • the diffuser polymer particles are produced using 0 to 50 wt% of other copolymerizable vinyl monomer(s).
  • the C 2-8 alkyl acrylate monomers is butyl acrylate.
  • the other copolymerizable vinyl monomer(s) is selected from alkyl methacrylates and monovinyl arenes.
  • the other copolymerizable vinyl monomer(s) is styrene.
  • Crosslinking monomers suitable for use in producing the diffuser polymer particles of the present invention include crosslinking monomers well known to those skilled in the art that are compatible with the other materials from which the diffuser polymer particles are produced.
  • the crosslinking monomers are selected from multi-ethylenically unsaturated monomers in which the ethylenically unsaturated groups have approximately equal reactivity; multi-ethylenically unsaturated monomers having two or more non-conjugated double bonds of differing reactivity; and combinations thereof.
  • the multi-ethylenically unsaturated monomers in which the ethylenically unsaturated groups have approximately equal reactivity are selected from divinylbenzene; glycol di- and trimethacrylates and acrylates; and triol triacrylates and methacrylates.
  • the crosslinking monomers are selected from butylene glycol diacrylates.
  • the multi-ethylenically unsaturated monomers having two or more non-conjugated double bonds of differing reactivity are selected from allyl methacrylate; diallyl maleate and allyl acryloxypropionate.
  • the crosslinking monomer is allyl methacrylate.
  • the crosslinking monomers include a combination of multi-ethylenically unsaturated monomers in which the ethylenically unsaturated groups have approximately equal reactivity and multi-ethylenically unsaturated monomers having two or more non-conjugated double bonds of differing reactivity.
  • the diffuser polymer particles are produced using post-cure reactions.
  • the post-cure reaction occurs when a copolymer is formed from a monomer having a pendant peroxide group, which is then activated by heating to a temperature higher than that used in the polymerization. The activated peroxide group will promote crosslinking of the diffuser polymer particles.
  • a second free-radical initiator can be added to the polymerization; this second initiator is selected to be stable under the initial polymerization conditions, but to be activated by, for example, exposure to light or increased temperature subsequent to the initial polymerization.
  • the diffuser polymer particles are prepared using any known polymerization technique suitable for use with the starting materials selected.
  • the preparation of the diffuser polymer particles involves preparing uniformly sized seed particles by emulsion polymerizing at least one monomer component of the diffuser polymer particles, swelling the seed particles with one or more monomer components of the diffuser polymer particles, and polymerizing the monomer within the swelled seed particles. The swelling and polymerizing steps can be repeated as necessary to provide diffuser polymer particles of the desired size.
  • the procedure for making the diffuser polymer particles involves emulsion polymerizing the seed particles using conditions that restrict the molecular weight of the polymer that forms, such as by including chain-transfer moderators, e.g., mercaptans, in the polymerization mixture, such that the resulting seed particles comprise an easily swellable oligomer.
  • This process may be varied by preparing the initial emulsion polymer particles in the absence of such limiting of the polymer molecular weight, but subsequently conducting one or more of the swelling and polymerizing steps using the conditions which restrict the polymer molecular weight. In this variation the initial emulsion polymer particles do not swell as readily as subsequent, larger particles having a lower overall molecular weight.
  • the light-scattering composition comprises a matrix polymer with diffuser polymer particles distributed therein, wherein the diffuser polymer particles comprise 0.1 to 40 wt% of the light-scattering composition. In some aspects of these embodiments, the diffuser polymer particles comprise 0.1 to 10 wt% of the light-scattering composition. In some aspects of these embodiments, the diffuser polymer particles comprise 0.3 to 5 wt% of the light-scattering composition.
  • the diffuser polymer particles have an average particle size of 0.3 to 1.9 ⁇ m. In some aspects of these embodiments, the diffuser polymer particles have an average particle size of 0.4 to 1.5 ⁇ m. In some aspects of these embodiments, the diffuser polymer particles have an average particle size of 0.5 to 1.3 ⁇ m. In some aspects of these embodiments, the diffuser polymer particles have an average particle size of 0.5 to 1.2 ⁇ m. In some aspects of these embodiments, the diffuser polymer particles have an average particle size of 0.5 to 1.0 ⁇ m. In some aspects of these embodiments, the diffuser polymer particles have an average particle size of 0.6 to 0.9 ⁇ m. In some aspects of these embodiments, the diffuser polymer particles have an average particle size of 0.8 to 0.9 ⁇ m.
  • the diffuser polymer particles exhibit a size distribution such that at least 90 wt% of the diffuser polymer particles fall within ⁇ 40% of the average particle size. In some aspects of these embodiments, the diffuser polymer particles exhibit a size distribution such that at least 90 wt% of the diffuser polymer particles fall within ⁇ 35% of the average particle size. In some aspects of these embodiments, the diffuser polymer particles exhibit a size distribution such that at least 90 wt% of the diffuser polymer particles fall within ⁇ 32% of the average particle size.
  • the diffuser polymer particles have a crosslinking density of >4 to 99 wt%. In some aspects of these embodiments, the diffuser polymer particles have a crosslinking density of 5 to 50 wt%. In some aspects of these embodiments, the diffuser polymer particles have a crosslinking density of 5 to 10 wt%.
  • the diffuser polymer particles have a refractive index at a center thereof (RI center ) that is less than a refractive index at a surface thereof (RI surface ).
  • the RI center is 0.003 to 0.4 units less than the RI surface .
  • the RI center is 0.008 to 0.1 units less than the RI surface .
  • the RI center is 0.01 to 0.05 units less than the RI surface .
  • the RI center is 0.01 to 0.03 units less than the RI surface .
  • the RI center of the diffuser polymer particles is 1.2 to 1.6. In some aspects of these embodiments, the RI center of the diffuser polymer particles is 1.4 to 1.5.
  • the RI center of the diffuser polymer particles is within ⁇ 0.003 to ⁇ 0.6 units of the refractive index of the matrix polymer. In some aspects of these embodiments, the RI center of the diffuser polymer particles is within ⁇ 0.003 to ⁇ ⁇ 0.05 units of the refractive index of the matrix polymer. In some aspects of these embodiments, the RI center of the diffuser polymer particles is within ⁇ 0.003 to ⁇ 0.04 units of the refractive index of the matrix polymer. In some aspects of these embodiments, the RI center of the diffuser polymer particles is within ⁇ 0.02 to ⁇ 0.04 units of the refractive index of the matrix polymer.
  • One of ordinary skill in the art given the specific teachings of this application will be able to select materials for the preparation of the diffuser polymer particles to provide said particles with the desired refractive index properties for use in combination with a particular matrix polymer.
  • the diffuser polymer particles are combined with the matrix polymers by any suitable, conventional technique. In some aspects of these embodiments, the diffuser polymer particles are combined with the matrix polymers by melt blending.
  • the light-scattering composition further comprises optional additives.
  • the optional additives are selected from conventional additives, including, for example, ultraviolet-light stabilizers, ultraviolet-light absorbers, soluble flame retardants, dyes, thermal stabilizers, impact modifiers, processing aids, flow aids, pigments and fluorescent whitening agents.
  • the light-scattering composition further comprises one or more impact modifiers.
  • the impact modifiers are selected to form clear, non-light-scattering blends with the matrix polymer.
  • the matrix polymer, diffuser polymer particles and optional additives are blended and extruded into pellets, which are then molded or extruded.
  • the matrix polymer, diffuser polymer particles and optional additives are processed into sheet or film.
  • the light-scattering compositions of the present invention can be used in a variety of applications including light diffusers in luminaires, rear projection screens for television or film viewing, decoration, illuminated signs (especially back-lit translucent signs), skylight, lighting fixtures (especially for fluorescent or incandescent lighting), greenhouse glazing, light boxes, drafting tables, automotive sunroofs, artistic applications (e.g., as visual display-case components), antiglow screens for CRT units, twin-wall glazing, liquid crystal displays, plasma displays, privacy windows, covers for automotive lights and coatings.
  • Diffusivity used in the Tables was obtained as the reciprocal of the integral of the output intensity versus the diffusing angle, measured by Goniophotometer and recorded as a percentage. On this scale a perfect diffuser would yield a diffusivity value of 100 percent.
  • This example illustrates the preparation of crosslinked polymer particles of 0.25 ⁇ m in diameter for making large seed particles in aqueous dispersion.
  • the mixtures noted in Table 1 were prepared with deionized water: Table 1 Mixture Component Parts by Weight A Water 180 Sodium Carbonate 0.40 B n -Butyl Acrylate 98.0 Allyl Methacrylate 1.75 1,4-Butanediol Diacrylate 0.25 22.5% aqueous Sodium Dodecylbenzenesulfonate 2.22 Water 40.8 C Sodium Persulfate 0.06 Water 11.9
  • a reactor equipped with stirrer and condenser and blanked with nitrogen was charged with Mixture A and heated to 83°C.
  • To the reactor contents was added 10% of emulsified Mixture B and 25% of Mixture C.
  • the temperature was maintained at 83°C and the mixture was stirred for 60 minutes, after which the remaining Mixture B and Mixture C were added to the reactor with stirring over a period of 120 minutes. Stirring was continued at 83°C for 90 minutes, after which the reactor contents were cooled to room temperature.
  • the particle size of the resulting particles was 0.25 ⁇ m as measured by a Brookhaven Instruments particle size analyzer BI-90.
  • Example 2 the particles in the emulsion of Example 1 are grown to 0.56 ⁇ m diameter using n -butyl acrylate, styrene, and 1-hexanethiol.
  • Table 2 Mixture Component Parts by Weight A Sodium Carbonate 0.08 9.76% aqueous Sodium Dodecylbenzenesulfonate 0.01 Water 156.00 B 30.10% aqueous emulsion from Example 1 29.80 C n -Butyl Acrylate 81.80 Styrene 18.20 9.76% aqueous Sodium Dodecylbenzenesulfonate 4.53 Water 57.50 D 1-Hexanethiol 18.80 9.76% aqueous Sodium Dodecylbenzenesulfonate 0.58 Water 15.00 E Sodium Persulfate 0.11 Water 47.40 F t -Butyl Hydroperoxide 70% 0.30 Water 15.00 G Sodium Form
  • Mixture A was added to the reactor of Example 1 and heated to 88°C with stirring. The air in the reactor was replaced by nitrogen. When the reactor temperature stabilized at 88°C, Mixture B was charged into the reactor. Emulsified Mixtures C and D, and Mixture E were then added to the reactor, with stirring, over a period of 300 minutes. Stirring was continued at 88°C for 90 minutes. The reactor contents were cooled to 65°C. Mixtures F and G were added and the reactor contents were maintained at 65°C with stirring for 1 hour, after which the reactor contents were cooled to room temperature. The resulting emulsion particles had a diameter of 0.56 ⁇ m as measured by a Brookhaven Instruments particle size analyzer BI-90.
  • Example 2 a procedure similar to Example 1 was used to prepare crosslinked polymer particles in aqueous emulsion containing 99.30 parts of n -butyl acrylate and 0.70 part of allyl methacrylate.
  • the resulting emulsion had a solids content of 32.52% and a particle size of 0.054 ⁇ m.
  • Example 2 In this example the procedures in Example 2 were repeated using an appropriate amount of an emulsion similar to Example 3 having a particle size of 0.24 ⁇ m .
  • the resulting emulsion had a particle size of 0.45 ⁇ m .
  • Example 2 In this example the procedures in Example 2 were repeated using an appropriate amount of an emulsion similar to Example 3 having a particle size of 0.054 ⁇ m .
  • the resulting emulsion had a particle size of 0.21 ⁇ m .
  • the polymers derived from this synthesis recipe are as follows:
  • Example 2 In this example the procedures in Example 2 were repeated using an appropriate amount of an emulsion similar to Example 3 having a particle size of 0.054 ⁇ m , replacing styrene with methyl methacrylate, and replacing 1-hexanethiol with 20 parts by weight of butyl 3-mercaptopropionate.
  • the resulting emulsion had a particle size of 0.21 ⁇ m.
  • Example 2 In this example the procedures in Example 2 were repeated using an appropriate amount of an emulsion similar to Example 3 having a particle size of 0.054 ⁇ m, adding 1.0 part by weight of methyl ⁇ -cylodextran in Mixture A, and replacing styrene with methyl methacrylate and 1-hexanethiol with 1-dodecanethiol.
  • the resulting emulsion had a particle size of 0.23 ⁇ m .
  • the resulting emulsion had a particle size of 0.21 ⁇ m.
  • the polymers derived from this synthesis recipe are as follows:
  • the particles in the emulsion of Example 2 are expanded to 5 ⁇ m diameter using n- butyl acrylate and ally methacrylate in Stage I which is then followed by Stage II copolymerization of methyl methacrylate and ethyl acrylate.
  • Example 1 To the reactor of Example 1 was added A which was heated to 90°C with stirring. The air in the reactor was replaced by nitrogen. When the reactor temperature stabilized at 90°C, Mixture B was charged into the reactor. Mixture C was emulsified with a homogenizer and charged into the reactor. The reactor was stirred at 60°C for 1 hour. Mixture D was emulsified with a homogenizer and charged into the reactor. After 1 hour agitation at 60°C, the reactor was gradually heated to 65-70°C while an exothermic polymerization takes place. After reach peak temperature, agitation was continued while the reactor was cooled to 73°C in 30 minutes. Charge half of Mixture F.
  • the particles in the emulsion of Comparative Example 8 are mixed with a polymer emulsion containing a methyl methacrylate / ethyl acrylate copolymer.
  • the mixtures noted in Table 4 were prepared: Table 4 Mixture Component Parts by Weight A Aqueous emulsion from Example 8 at 35.95% solids 250.35 B Aqueous emulsion of methyl methacrylate / ethyl acrylate copolymer at 45.00% solids 22.22 96 wt% methyl methacrylate / 4 wt% ethyl acrylate
  • Example 1 To the reactor of Example 1 was added A. With stirring at room temperature, B was added to the reactor. The stirring was continued for 15 minutes before the mixture was taken out of the reactor. Water was then evaporated off from the mixture to produce dried powder.
  • the test plates derived from injection molding are of the following dimension: 77mm x 56mm x 3mm.
  • the test plates, derived from injection molding, were of the following dimension: 77mm x 56mm x 3mm.
  • the test plates derived from injection molding are of the following dimension: 77mm x 56mm x 3mm.
  • the test plates derived from injection molding are of the following dimension: 77mm x 56mm x 3mm.
  • the test plates derived from injection molding are of the following dimension: 77mm x 56mm x 3mm.
  • Light diffuser beads of the compositions given in Table 10, were dry blended in polycarbonate resin (NAS-21; RI 1.57) followed by melt compounding in a Leistritz extruder at barrel temperature ranging from 200 to 224 °C. The melt compounding was followed by pelletization, drying,at 60 C in a vacuum oven, and injection molding at temperatures between 200 and 234 °C.
  • the test plates derived from injection molding are of the following dimension: 77mm x 56mm x 3mm.
  • the test plates derived from injection molding are of the following dimension: 77mm x 56mm x 3mm.
  • the test plates derived from injection molding are of the following dimension: 77mm x 56mm x 3mm.
  • the test plates derived from injection molding are of the following dimension: 77mm x 56mm x 3mm.
  • the test plates, derived from injection molding, were of the following dimension: 77mm x 56mm x 3mm.
  • the test plates, derived from injection molding, were of the following dimension: 77mm x 56mm x 3mm.
  • the test plates, derived from injection molding, were of the following dimension: 77mm x 56mm x 3mm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Optical Elements Other Than Lenses (AREA)
EP08250237A 2007-01-26 2008-01-18 Light-scattering compositions Active EP1950244B1 (en)

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Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI369379B (en) * 2007-01-26 2012-08-01 Rohm & Haas Light-scattering compositions
JP2010211171A (ja) * 2008-07-08 2010-09-24 Sumitomo Chemical Co Ltd 光拡散板及び面光源装置並びに液晶表示装置
US8119328B2 (en) * 2008-08-11 2012-02-21 Eastman Kodak Company Imaging element and method using differential light scattering
DE102009005273A1 (de) * 2009-01-20 2010-07-22 Mitja Jelusic Rückprojektionssystem, Verfahren zur Herstellung und Anwendung
KR20100120930A (ko) * 2009-05-07 2010-11-17 금호석유화학 주식회사 반사방지막 매립제용 공중합체, 그 제조방법 및 이를 포함하는 매립제 조성물
JP5386417B2 (ja) * 2010-01-08 2014-01-15 三菱エンジニアリングプラスチックス株式会社 ポリカーボネート樹脂組成物及びそれからなる成形品
EP2431423A3 (en) * 2010-09-21 2013-07-10 Rohm and Haas Company Anti-reflective coatings
EP2431422A3 (en) * 2010-09-21 2013-07-10 Rohm and Haas Company IR - reflecting compositions
EP2431424A3 (en) * 2010-09-21 2014-03-05 Rohm and Haas Company UV - reflecting compositions
JP5576756B2 (ja) * 2010-09-30 2014-08-20 積水化成品工業株式会社 光拡散性樹脂組成物および光拡散性部材
SG193617A1 (en) 2011-03-30 2013-11-29 3M Innovative Properties Co Hybrid light redirecting and light diffusing constructions
JP2012255135A (ja) 2011-05-17 2012-12-27 Rohm & Haas Co 熱可塑性ポリマーを吸収したラテックス粒子
CN102702711A (zh) * 2012-03-20 2012-10-03 李澄 以聚碳酸酯为基材的边缘融合用背投硬幕
TWI588199B (zh) * 2012-05-25 2017-06-21 羅門哈斯公司 光擴散聚合物組成物、製造該光擴散聚合物組成物的方法以及由之製得的物品
TWI583733B (zh) * 2012-08-10 2017-05-21 羅門哈斯公司 光擴散聚合物組成物、其製造方法,及由其製得之物件
TWI487754B (zh) 2012-09-18 2015-06-11 Rohm & Haas 水性塗層組成物及由其製造之具特殊光澤槪況之塗層
TWI513996B (zh) 2012-09-18 2015-12-21 Rohm & Haas 水性塗層組成物及由其製造之抗眩光塗層
CN103012966B (zh) * 2012-12-06 2016-06-01 上海日之升新技术发展有限公司 一种光扩散改性聚丙烯材料及其制备方法
US10053597B2 (en) 2013-01-18 2018-08-21 Basf Se Acrylic dispersion-based coating compositions
WO2014159970A1 (en) * 2013-03-13 2014-10-02 Orafol Americas Inc. Photometrically adjustable diffuser
AR095055A1 (es) * 2013-03-25 2015-09-16 Rohm & Haas Película anti-reflejo para matrices fotovoltaicas
TWI522412B (zh) * 2013-03-25 2016-02-21 羅門哈斯公司 包裝用途之半透明聚烯烴膜
CN104369564B (zh) * 2013-08-13 2019-06-11 罗门哈斯公司 具有改善的初始对比度的热记录材料
US20160303025A1 (en) * 2013-12-09 2016-10-20 Rohm And Haas Company Llc Skin care compositions containing light diffuser polymeric beads
TWI668112B (zh) * 2014-02-11 2019-08-11 美商陶氏全球科技有限責任公司 用於增強聚烯烴薄膜之無光澤外觀的丙烯酸系珠粒
TWI713446B (zh) * 2014-04-15 2020-12-21 美商陶氏全球科技有限責任公司 經增強的觸覺反應性及光學半透明性包裝用膜
MX2016016864A (es) * 2014-06-19 2017-05-10 Dow Global Technologies Llc Cuentas acrilicas para mejorar la termicidad de peliculas de efecto invernadero.
CN104650566A (zh) * 2015-01-13 2015-05-27 安徽泰诺塑胶有限公司 一种用于生产汽车灯罩的聚碳酸酯的聚碳酸酯复合材料的制备方法
WO2017030851A2 (en) * 2015-08-20 2017-02-23 Oletquin Management Llc Fabric with embedded electrical components
CN105754039B (zh) * 2016-02-26 2018-07-10 王金明 一种聚4-甲基-1-戊烯光扩散剂及其制备方法
US11589518B2 (en) 2018-10-18 2023-02-28 Trinseo Europe Gmbh Light diffuser for horticultural lighting
KR102426179B1 (ko) * 2019-05-02 2022-07-28 기후변화대응 에너지전환 협동조합 태양광 모듈이 광산란부를 포함하는 투명지붕부에 배열된 채광 온실

Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7904249A (nl) 1978-06-20 1979-12-27 Cancer Res Nat Found Nieuwe cyclische acetalen met cytostatische, bloed- drukverlagende en pijnstillende werking, werkwijze ter bereiding van deze verbindingen alsmede farmaceu- tische preparaten die een dergelijke verbinding bevat- ten.
US5237004A (en) 1986-11-18 1993-08-17 Rohm And Haas Company Thermoplastic and thermoset polymer compositions
FR2639266A1 (en) * 1988-11-22 1990-05-25 Commissariat Energie Atomique Process for the manufacture of a suspension of gold microparticles which have a mean diameter in the range from 0.1 to 0.5 mu m and monodisperse suspension obtained by this process
JPH04342750A (ja) * 1991-05-17 1992-11-30 Asahi Chem Ind Co Ltd 着色性の優れた耐候性、耐衝撃性重合体組成物
US5237007A (en) 1992-03-09 1993-08-17 Novacor Chemicals (International) S.A. Clear tough alloys
DE4229642A1 (de) * 1992-09-04 1994-03-10 Bayer Ag Pulvermischungen für matte Polycarbonat-Formmassen
GB9314604D0 (en) * 1993-07-14 1993-08-25 Dow Deutschland Inc Light diffuser composition
DE4443966A1 (de) * 1994-12-09 1996-06-13 Basf Ag Thermoplastische Formmassen
DE19503545A1 (de) * 1995-02-03 1996-08-08 Basf Ag Teilchenförmige Pfropfcopolymerisate und diese enthaltende thermoplastische Formmassen mit verbesserter Einfärbbarkeit
JPH10237261A (ja) * 1997-02-27 1998-09-08 Mitsubishi Rayon Co Ltd 艶消しアクリルフィルムおよびアクリルフィルムを積層した艶消し成形品
JP3358520B2 (ja) * 1997-12-09 2002-12-24 住友化学工業株式会社 ポリオレフィン改質用微粒子
WO2002062890A1 (en) 2001-02-06 2002-08-15 Cyro Industries Polymethylmethacrylate compositions of enhanced optics and low temperature impact strength
JP2003347997A (ja) 2002-05-27 2003-12-05 Nippon Telegr & Teleph Corp <Ntt> アンテナ装置および無線通信システム
JP2004023218A (ja) 2002-06-13 2004-01-22 Matsushita Electric Ind Co Ltd 電話装置
JP4518733B2 (ja) 2002-06-17 2010-08-04 ソニー株式会社 窒化ガリウム系半導体レーザ素子の製造方法
JP2004026612A (ja) 2002-06-28 2004-01-29 Koa Corp セラミック用表示材料
DE10229732A1 (de) 2002-07-02 2004-01-22 Basf Ag Optische Anzeigeelemente auf Basis wässriger Polymerdispersionen
DE10320318A1 (de) 2003-05-06 2004-12-02 Röhm GmbH & Co. KG Verfahren zur Herstellung von lichtstreuenden Formteilen mit hervorragenden optischen Eigenschaften
US20050049368A1 (en) 2003-09-02 2005-03-03 Mitsubishi Engineering-Plastic Corporation Aromatic polycarbonate resin pellets for light guide plate, light guide plate, method for producing light guide plate and surface light source unit using the same
JP2005112971A (ja) 2003-10-07 2005-04-28 Sumitomo Chemical Co Ltd 樹脂組成物および積層樹脂板
JP2005140863A (ja) 2003-11-04 2005-06-02 Nitto Denko Corp 粒子分散系樹脂シート、画像表示装置用基板および画像表示装置
JP2005213410A (ja) 2004-01-30 2005-08-11 Nippon Zeon Co Ltd 高屈折率樹脂組成物
JP4263113B2 (ja) 2004-01-30 2009-05-13 積水化成品工業株式会社 複合樹脂粒子とその製造方法、光拡散性樹脂組成物、光拡散性材料、および液晶ディスプレイ用バックライトユニット
JP2005220157A (ja) 2004-02-03 2005-08-18 Dainippon Ink & Chem Inc 硬化膜及び硬化膜からなる機能性媒体
US7440045B2 (en) * 2004-06-11 2008-10-21 Hannstar Display Corporation Flat panel display having a brightness enhancement diffuser plate with two diffusing layers
US20060003239A1 (en) 2004-06-30 2006-01-05 Cooper Terence A Multilayer optical display device
JP2006023350A (ja) 2004-07-06 2006-01-26 Fuji Photo Film Co Ltd 反射防止フィルム、偏光板、および画像表示装置
JP2006030839A (ja) * 2004-07-21 2006-02-02 Sumitomo Dow Ltd ポリカーボネート樹脂製光拡散板
JP2006084927A (ja) 2004-09-17 2006-03-30 Gantsu Kasei Kk 光拡散剤およびその製造法
US7541401B2 (en) 2004-12-31 2009-06-02 Cheil Industries Inc. Impact modifier for a polymer composition and method for preparing the same
TWI369379B (en) * 2007-01-26 2012-08-01 Rohm & Haas Light-scattering compositions

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CN102532791A (zh) 2012-07-04
KR100957040B1 (ko) 2010-05-13
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CN101230179A (zh) 2008-07-30
JP5065923B2 (ja) 2012-11-07
US20110105677A1 (en) 2011-05-05
US20080182958A1 (en) 2008-07-31
KR20080070533A (ko) 2008-07-30
US8084543B2 (en) 2011-12-27
TWI386448B (zh) 2013-02-21
DE602008005353D1 (de) 2011-04-21
TW200844165A (en) 2008-11-16
JP2008195935A (ja) 2008-08-28
US7893162B2 (en) 2011-02-22
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TWI369379B (en) 2012-08-01
EP1950244A1 (en) 2008-07-30
JP2012162747A (ja) 2012-08-30

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